Soluble onium salts of halogenmethylated thioindigos



Patented Feb. 12, 1952 SOLUBLE ONIUM SALTS OF HALOGEN- METHYLATED THIOINDIGOS- David I. Randall and Carl M. Smith, Easton, Pa.,

assignors to General Aniline & Film Corporation, New York, N. Y., a corporation of Dela- Ware No Drawing. Application December 30, 1949, Serial No. 136,154

6 Claims. Cl- 260-332) This invention relates to the manufacture of new dyestuffs from the halogenmethyl derivatives of thioindigoid dyes.

In our copending application Serial No. 135,518, filed December 28, 1949, now U. S. Patent No. 2,545,497, issued March 20, 1951, we have described the halogenmethyl derivatives of thioindigos and their preparation. It was pointed out in said application that the halogenmethyl derivatives of some of the thioindigos have substantive dyeing properties and that all of the halo- Ai(CH:Cl)n+nNHiCSNH: Ar GHzSC where Ar is the radical of a thioindigo compound and n. is an integer from 1 to 3. The thiourea may be replaced by thiourea derivatives such as l-allylthiourea, l-methylthiourea, l-phenylthiourea, 1,3-dimethyl-1, 1,3-ethylene-, 1,1,3-trimethyl-,

and 1,1,3,3-tetramethylthiourea. The trimethylamine may be replaced by tertiary amines such as pyridine, picoline, isoquinoline, quinoline, di-

ethylaminoethyl alcohol, triethylamine, and

benzyldimethylamine.

The more soluble and the more desirable isothiouronium salts are those derived from trimethyland tetramethylthiourea. To insure sufficient solubility, it' is necessary that the halogenmethylated thioindigo contain on the average at least one halogenmethyl group. Prints made from the isothiouronium salts of the chlormethylated thioindigos exhibit bright shades and possess excellent fastness to chlorine, washing, and light. The prints obtained from the pyridinum salts of the chlormethylated thioindigos exhibit fair fastness to chlorine and washing, but are inferior to the isothiouronium salts in light fastness.

The isothiouronium salts of the chlormethylated thioindigos are prepared by heating the chlormethylated thioindigo in a paste form with thiourea or a thiourea derivative over a steam bath with additions of water and frequent stirrin for a period of about one hour. The reaction mixture is then diluted with acetone or water, filtered, and slurried or washed with acetone. The product is air dried. The resulting dyes are water soluble and are substantive to paper; cotton, silk, nylon, and W001. They may be paste printed on cotton, silk, and nylon, and. developed by vat or acid aging methods well known to the art. The isothiouronium salts of the thioindigos may be represented by the formula:

Ar OHgSC wherein Ar is the radical of a thioindigo compound; R1, R2, R3, and R4 are members of the group consisting of alkyl, alkylene, aryl and hydrogen, of which R2 and R4 may together form a closed ring system; 11, is an integer from 1 to 3; and A indicates a negative ion, such as chlorine, bromine, or sulfate.

The quaternary salts of the chlormethylated thioindigos are prepared by entirely heating the chlormethylated thioindigo with a tertiary amine. The resulting quaternary salts may be represented by the formulae:

Ar(OHzNQ1Q2QsA)" wherein A! has the same meaning as above; Q1, Q2, and Q3 are members of the group consisting of alkyl, alkylol, and alkaryl; Z indicates the C atoms necessary to complete a 6-membered ring system; A and n have the same meanings as above. Print dyeings may be made from these quaternary salts of the chlormethylated thioindigos in the same manner as in the case of the isothiouronium salts and will dye directly from bath with additions of Water and frequent stiraqueous solutions. Both the isothiouronium and ring the reaction mixture was diluted with acequaternary salts are also useful as bactericides. tone and triturated twice with more acetone, filfungicides, and insecticides. tered and washed with acetone and dried in a As starting materials for the production of the vacuum desiccator. Yield=3.8 g. purple powder, isothiouronium and quaternary salts, the class of 5 completely soluble in water which gave attracchlormethylated thioindigos described in our 00- tive violet prints. The isothiouronium product pending application Serial No. 135,518, filed Dehas the formula:

(CHg)gN CHa /N(CH5)1 cember 28, 1949, are preferred. This class may be represented by the formulae:

( A mixture of 3.0 parts by weight of dichloromethyl-A-2,2' (3,3) binaphtho[2,1 blthio- 5 phen-3-one, obtained by the process of our co- Example 2 2 "(011201) pending application Serial No. 135,518, filed De- \S S/\;\ Y Y cember 28, 1949 and acetone was ballmilled to a fine dispersion and mixed into a casserole and 2 the acetone evaporated. Water was added and o 8 4.0 parts by weight trimethyl thiourea. The H mass was heated and stirred on the steam bath for one hour. It became very thick and dark Home in color. The mix was then diluted with acel l as tone, twice triturated with acetone, filtered, and

washed with acetone. Yield=4.0 g. dark brown powder almost completely soluble in water giving sharp clean brown prints. This isothiowherein R is a fused S-membered hydrocarbon uronium Product has the formula:

4. ore113 M 1101 o1 cs GH omso 01 CH HN NHCH:

ring system; n and n' are integers from 0 to 2; X and Y are members of the group consisting n f 25 'i gg gig 3 322 g i teger mm In a casserole on the steam bath 21.0 parts by m les will serv to further weight of dichlolomethyl dichloroillgs tjat i iivifiioi but are not intended to 55 7)7"dimeth1thiindig0, Obtained y e process in any way limit its scope. Unless otherwise of 0111' copending application S O- 135,518. stated, the parts are by weight. filed December 28, 1949, as a paste was stirred Example 1 with 30.0 parts by weight of dimethyl thiourea.

The mass rapidly thinned up, but after three In a casserole Parts by Weight of "f hours had become very thick. It was diluted 9 Y thlo" with hot water and filtered; the filtrate and fig ig gifg zg gi fi i g ig g g E 22 $5553" washings evaporated and thrown into acetone on a Waring Blendor. After filtering and re- .5 h'eated on a steam bath The paste rapidly and air dried. Y1eld=8.5 g. violet powder givthinned out and changed shade from Brilliant Scarlet to purple. After one hour on the steam has the formula:

Example 3 ing violet prints. This isothiouronium product Example 4 A mixture of 15.0 parts by weight chloromethyl-9-chloro-2-[5-bromo 3 0x0 2(3) indolylidenelnaphthol1,2-blthiophen 3 one, obtained by the process of our copending applica- After stirring rapidly V2 hour, the. precipitated i' sothiou-ronium salt is filtered ofi and washed with acetone. On. printing cotton strong shades of. pink of excellent :iastness to wash and chlorine are obtained. This product has. the formula:

02 61 .cscm

v o o CHSH tion Serial No. 135,518, filed December", 1949, 25.0 Example 7 parts by weight dimethyl thiourea and suificient water to make a paste was tumbled in a bottle 0 parts of chloromethyl t with stones for 1 hour. The paste was then rinsed into a casserole on a steam bath and heated for one hour with frequent stirring. The

product was slurried twice in a Waring Blendor with acetone, filtered and air dried. Yield=l'7.0 g. blue grey powder almost completely soluble in water giving grey blue prints. This isothiouronium product has the formula:

l Br

(Alternative entering positions) on jincna NHCH;

Example 5 A reaction mixture, consisting of 5 g. of 5,5,6,6'- tetramethyl 7,7 chloromethylthioindigo, obtained by the process of our copending application Serial No. 135,518, filed December 28, 1949, 8 g. of 1,1,3,B-tetramethylthiourea and 80 ml. of water, was heated at 90 C. for one hour and then cooled. The product was precipitated by the slow addition of 400 ml. of acetone; 8.9 g. It prints cotton in strong bright violet shades with good fastness properties. A mixture of 60% of this compound and 40% of Alcian Blue prints cotton in bright blue shades of excellent fastness. This isothiouronium product has the formula:

0 o 0133- CH3 CH3 on: s s

im m),

(LE2 U ah Example 6 heated under reflux for ten minutes.

bianthra [2,1,9cdel -thionaphthene-5-one, -ob'- tained by the process of our copend-ing applica'-' tion Serial No. 135,518, filed December 28, 1949, are mixed with 135 g. of 1,3-dimethyl thiourea and 500 m1. of water, mechanically stirred and The resulting green solution is cooled to 50 C. and then poured into 1000 m1. acetone. Collecting the precipitated green solid on a filter, washing several times with acetone, drying by exposure and hammernilling yields 100 g. of product. It prints cotton from an aqueous solution a bright green color of good fastness to light, chlorine, and washing. This product has the formula:

NHCH! We claim:

1. The soluble onium salts of halogenmethylated thioindigo dyes of the class consisting of those having the formulae:

wherein Ar is the radical or a thioindigo compound; R1, R2, R3, and R4 are members of the group consisting of aikyl, aikylene, phenyl and hydrogen of which R2 and R4 may together form a closed ring system; Q1, Q2, and Q: are members of the group consisting of alkyl, alkylol, and benzyl; Z indicates the C atoms necessary to complete a 6-membered ring system selected from the group consisting of pyridine, picoline, isoquinoline and quinoline; A is selected from the group consisting of chlorine, bromine and sulfate; and n is an integer from 1 to 3.

2. The isothiouronium salt of chlormethylated c395: imam cscn, 0 o cmsc 61 OHaHN HCH;

4,4'-dimethyl-6,6'-dichloro thioincligo having the formula:

011921 3 CH3 CH3 imam Cl osmo o o 1 cmsc C1 CHJHN EUR;

01 S 8 Cl 3. The isothiouronium salt of chlormethylated A-2,2(3,3')-binaphthol[2,1-6llthiophen 3 one having the formula:

0mm: M0119:

4. The isothiouronium salt of chlormethylated 5,5-dichloro-7,7-dimethylthioindigo having the formula:

5. The isothiouronium salt of chlormethylated 5,5-6,6'-tetramethy1thioincligo having the formula:

DAVID I. RANDALL. CARL M. SMITH.

No references cited. 

1. THE SOLUBLE ONIUM SALTS OF HALOGENMETHYLATED THIOINDIGO DYES OF THE CLASS CONSISTING OF THOSE HAVING THE FORMULAE: 